Detergent compositions and detergent adjuvant combinations thereof, and processes for forming the same

ABSTRACT

Detergent compositions and detergent adjuvant combinations thereof and processes for forming the same are provided, the adjuvant combination comprising an alkaline hydrated silica pigment precipitate and electrolyte, the electrolyte being selected in a controlled proportion from the class of alkali metal carbonates and/or bicarbonates, and the adjuvant being combined with soap and/or other anionic and/or non-ionic detergents and/or polymeric emulsifiers in the composition. The silica pigment precipitate may be formed in the presence of the detergent, and detergent may be added to or be formed in the presence of the adjuvant combination. The products may be dried to form concentrated liquid, paste, bar, and powdered detergent compositions, the latter preferably being spray dried.

United States Patent 1191 1111 3,886,079 Burke, Jr. May 27, 1975 [54]DETERGENT COMPOSITIONS AND 3,630,919 12/1971 Sheaffer 252/88 DETERGENTADJUVANT COMBINATIONS 3,630,929 12/1971 Van Dljk 252/136 3,708,428 l/1973 MacDonald 252/109 THEREOF, AND PROCESSES FOR FORMING THE SAME OTHERPUBLICATIONS Synthetic Detergents, by A. Davidsohn et al., Leonard Hill,London 1967, pp. 37, 38 & 53.

Primary ExaminerP. E. Willis, Jr. Attorney, Agent, or Firml-Iall &Houghton [5 7] ABSTRACT Detergentco mpositions and detergent adjuvantcombinations thereof and processes for forming the same are provided,the adjuvant combination comprising an alkaline hydrated silica pigmentprecipitate and electrolyte, the electrolyte being selected in acontrolled proportion from the class of alkali metal carbonates and/orbicarbonates, and the adjuvant being combined with soap and/or otheranionic and/or non-ionic detergents and/or polymeric emulsifiers in thecomposition. The silica pigment precipitate may be formed in thepresence of the detergent, and detergent may be added to or be formed inthe presence of the adjuvant combination. The products may be dried toform concentrated liquid, paste, bar, and powdered detergentcompositions, the latter preferably being spray dried.

21 Claims, 1 Drawing Figure PRSMRATIOH 01 12mm ADJUVAIVI COMMITIOIB ofSodium Carbonate and/or Bicarbonate and weed Alkaline Silica Pigments ,2REGION "A" 3 h-eferrod.

3 Ranges 0 e l 1.5 l l g \4- Precipitation Region l 4- moctrolyte tarmngRegion 1011. 00 per r1101. x6 0 or an emic/ PATENTEmiz-wzv ms 3.886; 079

HEPARATION OF DETERGENT ADJ'U'VANI' COMPOSITIONS of Sodium Carbonateand/ or Bicarbonate and Hydrated Alkaline Silica Pigments REGION "B"Most Preferred Ranges 3.0 b

A: REGION "A" 3 Preferred 3 Ranges 3 n a u z 1.5 o \4- Hecipitation 2Region Electrolyte forming Region Male. co per mol Na o of Na O(SiONVENTOR (f ir-7,- fa m/1. R

ATTORNEY 1 DETERGENT COMPOSITIONS AND DETERGENT ADJUVANT COMBINATIONSTHEREOF, AND PROCESSES FOR FORMING THE SAME BACKGROUND OF THEINVENTION 1. Field of the Invention The field of this invention pertainsto detergent compositions (class 252-89) and detergent adjuvants thereofand processes for forming the same.

2. Description of the Prior Art The phosphates commonly employed indetergent compositions have caused environmental pollution and it hasfor some time been desired to obtain detergent compositions anddetergent adjuvants having reduced or no phosphate content, atreasonable costs, and the present invention aims to satisfy this want.

OBJECTS AND SUMMARY OF THE INVENTION A first object of the presentinvention is to provide a detergent adjuvant consisting essentially ofalkaline hydrated silica pigment precipitate prepared with the aid ofcarbon dioxide and/or an alkali metal bicarbonate and having a boundalkali content and a free alkali electrolyte content, and the lattercomprising alkali metal carbonate and/or bicarbonate, such adjuvantbeing combined with or suitable for combination with detergents from theclass consisting of soaps, synthetic anionic detergents, non-ionicdetergents, polymeric anionic and non-ionic dispersants or emulsifyingagents, and combinations of the same, for assisting the detergent actionthereof.

A second object of the invention is to provide improved detergentcompositions by combining such detergent adjuvant in never dried formwith detergent material selected from the class consisting of soaps,synthetic anionic detergents, non-ionic detergents, polymeric anionicemulsifying agents and combinations of the same.

A third object of the invention is to prepare such detergent adjuvant byreacting alkali metal silicate solutions with carbon dioxide and/oralkali metal bicarbonates in the presence of an aqueous solution ofdetergent selected from the class consisting of soaps, synthetic anionicdetergents, non-ionic detergents, polymeric emulsifying agents andcombinations of the same.

In its process aspect the invention comprises a process for preparing adetergent adjuvant combination which comprises:

a. forming an aqueous solution of water soluble alkali metal silicate,

b. adding to said solution sufficient reactant selected from the classconsisting of carbon dioxide and alkali metal bicarbonate to formthereof a solution of electrolyte selected from the alkali metalcarbonates and bicarbonates and having a precipitate of alkaline silicapigment therein, and

c. recovering said alkaline silica pigment and at least 25% dry basis,by weight, of the electrolyte resulting from step (b), in combination,as a detergent adjuvant combination.

' Silica pigment containing bound alkali.

In such three step process, step (b) may be conducted to provide saidsolution with electrolyte containing predetermined significantproportions of alkali metal bicarbonate, e.g. in the range of at least 2mol percent to at least 90 mol percent thereof; the quantity of water ofthe solution may be reduced after the formation of the precipitate instep (b); in step (c) the recovery may include spray drying; in step (c)substantially all of the electrolyte of the solution may be recovered aspart of said detergent adjuvant combination; and in step (c) thedetergent adjuvant combination may be mixed with detergent materialselected from the class consisting essentially of the water solublemembers of the following groups: Group (I) soaps; Group (ll) syntheticanionic detergents; Group (lll) anionic polymeric emulsifiers; Group(IV) non-ionic detergents: Group (V) non-ionic polymeric emulsifiers;and combinations of two or more of said members; in a ratio in the rangeof 5:95 to :5 parts dry basis, by weight, based on the silica content asSiO and the product recovered may be a detergent compositionincorporating the detergent adjuvant combination. Furthermore, in step(c) the detergent adjuvant combination, without having been driedfollowing step (b), may be mixed with an aqueous dispersion of thedetergent material selected from the class consisting essentially of thewater soluble members of said groups and combinations of said members;in a ratio in the range of 5:95 to 95:5 parts dry basis, by weight,based on the silica content as SiO and dried therewith to form theproduct which may be spray dried when a powdered product is desired. Inpreparing the composition in step (c) detergent material selected fromthe sub-class consisting of the members of Groups (I), (ll) and (ll!)may be formed in the presence of the silica pigment by reaction of thecorresponding free acid with alkalinity of the combination resultingfrom step (i); and detergent materialcomprising a soap may be formed inthe presence of the silica pigment by saponification of a fatty acidglyceride with the aid of alkalinity of the combination resulting fromstep (b). In further embodiments of the invention in step (a) theaqueous solution of water soluble alkali metal silicate may containdetergent material selected from the class consisting essentially of thewater soluble members of the following groups: Group (I) soaps; Group(ll) synthetic anionic detergents; Group (lll) anionic polymericemulsifiers; Group (IV) non-ionic detergents; Group (V) non-ionicpolymeric emulsifiers; and combinations of two or more of said members;in a ratio 5:95 to 95:5 parts, dry basis, by weight, based on the silicacontent of the solution as SiO and the product recovered may be adetergent composition incorporating the same with the detergent adjuvantcombination; and in this embodiment in step (a) less than the maximumratio of detergent to silica may be employed, and in step (c) thedetergent adjuvant combination may be mixed with further detergent,material selected from the members of said class and combinationsthereof, in an amount which combined with that included in step (0) liesin the aforesaid ratio range.

In its product aspect the invention provides a composition comprising adetergent adjuvant combination consisting essentially of:

a. a silica pigment, and

b. an electrolyte,

c". said silica pigment being an alkaline hydrated silica pigment whichhas been prepared by the acidulation of aqueous sodium silicate solutionwith the aid of reactant selected from the class consisting of carbondioxide and the alkali metal bicarbonates,

d. said electrolyte being selected from the class consisting of thealkali metal carbonates and bicarbonates.

e. said combination comprising by weight from 0.1 to

20 parts of said electrolyte per part of silica pigment, as SiO and f.said composition having been dried; and the electrolyte thereof maycomprise alkali metal bicarbonate in predetermined significantproportions, e.g. in the range of at least 2 mol percent to at least 90mol percent thereof.

Precipitated silica having bound alkali.

Furthermore the composition may be in the form of a spray dried powderwith the advantages of such form; and may comprise a mixture of saiddetergent adjuvant combination with detergent material selected from theclass consisting essentially of the water soluble members of thefollowing groups: Group (l) soaps; Group (II) synthetic anionicdetergents; Group (III) anionic polymeric emulsifiers; Group (IV)non-ionic detergents; Group (V) non-ionic polymeric emulsifiers; andcombinations of two or more of said members, in a ratio in the range of5195 to 955 parts dry basis, by weight, based on the silica content ofthe adjuvant combination as SiO and the product may comprise hydratedsilica pigment (and at least a part of said electrolyte) which has beenprepared in the presence of the detergent material.

In other embodiments the product may comprise the anionic detergentformed by reacting, in the presence of the precipitated silica pigment,the water insoluble anionic detergent free acid with alkali derived inthe preparation of said pigment; and the total detergent in the productmay comprise at least 5 parts per 100 dry basis by weight of detergentsselected from particular anionic ones of the aforesaid groups.

BRIEF DESCRIPTION OF THE DRAWINGS In the accompanying drawing the singleFIGURE is a chart illustrating the preferred and most preferred rangesof reactants for preparing detergent adjuvant combinations of theinvention.

DESCRIPTION OF PREFERRED EMBODIMENTS In preparing the detergent adjuvantin accordance with this invention commercially available alkali metalsilicates may be employed, i.e. sodium silicates of the weight ratio lla O/(SiO in which the ratio of sodium oxide to silicon dioxide mayrange from 1:0.48 to l:3.75 with the soluble glass range 111.6 to 123.75being preferred and the most preferred range being 123.0 to l:3.5e.g.3.22 in the 41 Be sodium silicate of commerce (see FIG. I).

Acidulation of the sodium silicate for forming detergent adjuvant ofthis invention is carried out in aqueous solution with the aid of carbondioxide and/or alkali metal bicarbonate eg. sodium bicarbonate, and ashereinafter exemplified water soluble alkali metal salts may be includedin the solution in the range of from O to 4 mols per mol of alkalinityof the sodium silicate as Na O. for regulating the particle size of thesilica pigment product. Such salt may be recovered as part of thedetergent adjuvant and when the salt so employed is alkali metalcarbonate its recovery correspondingly increases the alkalinity of theadjuvant combination.

Such acidulation may be applied to alkali metal silicate solutionshaving concentrations of alkali metal silicate-formula M O(SiO in whichM is alkali metal--in the range of about 20 grams per liter to about 200grams per liter, and may be carried out at temperatures between thefreezing point and boiling point of water, i.e. from about 5 to about C.at atmospheric pressure, or up to 200 C. or more if conducted underhigher pressures, and with or without the initial or timed addition ofelectrolyte.

The carbon dioxide gas employed in this invention may be full strengthor may be diluted with air or other inert gases, e.g. such as the dilutecarbon dioxide gas produced by the combustion of hydrocarbons such aspropane or butane.

The process of this invention may be conducted in a batchwise orstepwise manner, or continuously, depending on available equipment.

The FIGURE sets forth at A a region bounded by a, a, a", and a in whichthe detergent adjuvant of this invention is preferably produced, i.e. atthe bottom of the preferred range aqueous sodium silicate solution ofthe composition Na O(SiO at about 5% concentration, by weight, will formelectrolyte and precipitate alkaline hydrated silica pigment when saidsolution has been acidified with the addition of about 0.7 to 0.8 molsof carbon dioxide (point a) and, to reduce the alkalinity of theprecipitated pigment and its serum, further carbon dioxide may be addedand the electrolyte sodium carbonate can be converted in whole or inpart to sodium bicarbonate as indicated along line a-a'. At the top ofthis preferred range aqueous sodium silicate solutions of thecomposition Na O(SiO will form sodium carbonate electrolyte andprecipitate alkaline hydrated silica pigment when said solution isacidified with 0.4 to ()5 mols of carbon dioxide, as indicated at pointa". Likewise for this precipitate the alkalinity may be converted inwhole or in part through sodium carbonate to sodium bicarbonatedepending on the extent of carbonation as indicated along line a"a"'.

The size of the silica particles may be regulated during the preparationof the alkaline silica pigment.

As shown in the drawing, when one mole of sodium silicate of thecomposition Na O(SiO (lying at the point of ordinate value 3.22,abscissa value 0, at the left side of the drawing) is aciduated withabout 0.6 moles of carbon dioxide so that about 60% of the Na O isconverted to Na CO then at ordinate value 3.22 and abscissa value 0.6alkaline silica pigment will have precipitated at about (Na O)0,4(SiOi.e. Na O(SiO2)a.05, and the weight of bound alkali will be (Na O/NaO(Si- O )8.O5)( 100), equalling (62/545)(100) or about ll.4% by weightas Na O; and if the acidulation with carbon dioxide is carried to thepoint where one mole of CO has been reacted per mole of Na O and sodiumbicarbonate is beginning to form in the serum, at about ordinate value3.22 and abscissa value 1.0 which falls on the line b-b" in the drawing,then the bound alkali of the alkaline silica pigment precipitate will beabout 2% by weight as Na O; and if the acidulation with carbon dioxideis continued until the sodium carbonate in the serum is converted tosesquicarbonate (ordinate value 3.22 and abscissa value l.5) then thebound alkali of the silica pigment will be in the range of 1% by weightas Na O. When the adjuvant alkaline silica pigment precipitate isprepared from sodium silicate of the formula N21 O(SiO H2 treated withCO until the precipitated silica has a bound alkali content of 2% byweight as Na O, and the resulting alkaline pigment slurry is driedwithout separating any of the liquor from the alkaline silica pigment"slurry, the dried detergent adjuvant combination will contain boundalkali and free alkali in thefamount of about 35 weight as sodiumcarbonate.

Table A shows the calculated composition (dry basis) of the preferreddetergent adjuvant products depending on the ratio of Na O to SiO in thesodium silicate solution, and the degree of carbonation effected. Thequantity of sodium carbonate in the product can be varied at will and aquantity of sodium bicarbonate included if it is desirable to lower thepH, as above described.

TABLE A Sodium Silicate Composition Product Weight 70 Na O(SiO 1 mole C2 moles CO SiO Na CQ SiO NaHCO These calculated figures are on ananhydrous basis and have not been corrected for bound alkali.

0 NaO- ('s'i-o) -si-ona.

in which n=50.6 and the weight ratio of Na O/SiO is 2/98.

The pigment in addition to the aforesaid silica and bound alkali contenthas about 8% bound water which is removable by heating the pigment to1000 C.

The sodium silicate employable herein is represented by the formula NaO(SiO in which x lies in the range of 0.48 to 3.5 and when such sodiumsilicate is acidulated with carbon dioxide until the silica pigmentforms then such pigment can have a bound alkali in range of 02-40% byweight based on the silica content of the pigment as SiO and further thepigment can have a bound water content of about 515% by weight or morebased on the silica content of the pigment as SiO In the adjuvantcombination of silica and sodium carbonate and/or sodium bicarbonate andin the detergent combinations of detergent and silica and sodiumcarbonate and/or sodium bicarbonate the bound alkali content of thesilica is essential as it provides a means of removing heavy metal ionsfrom the water of the cleansing operation. Thus the alkali metal ion,i.e. the sodium ion of the bound alkali exchanges with the heavy metalion, thus the more hydratable and more soluble sodium ion of the silicais replaced by the less hydratable and less soluble heavy metal ion,i.e. by the calcium or magnesium ion.

In contrast a silica pigment which has been treated with acid and/orheavy metal salt and hasv no residual bound alkali no longer possessesthe property of being able to remove heavy metal ions from the aqueousphase and thus cannot reduce the hardness of water as such hardness maybe present in the cleansing operation.

The detergent materials with which the detergent ad- 5 juvant of thepresent invention may be used, and which may be combined therewith toform detergent compositions of the invention, are selected from theclass consisting essentially of the water soluble members of thefollowing groups: Group (I) soaps; Group (II) synthetic anionicdetergents; Group (III) anionic polymeric emulsifiers; Group (IV)non-ionic detergents; Group (V) non-ionic polymeric emulsifiers; andcombinations of two or more of said members; and may be combined withthe adjuvant in a ratio in the range of 5:95 to :5 parts dry basis, byweight, based on the silica content of the adjuvant combination as SiOBy the term soap is meant the alkali metal salts, amine salts, andammonium salts of carboxylic acids (herein termed corresponding freeacids) having from lto l0 carboxylic acid groups and having at least onecarboxylic acid group attached to a chain of from 8 to 36 carbon atoms.Carboxylic acids meeting this definition are exemplified by thefollowing: the fatty acids and the rosin acids and derivatives thereof,which have from 1 to 10 carboxyl groups and a chain of from 8 to 36carbon atoms attached to at least one carboxyl group thereof, and suchlong-chain carboxylic acids include the individual fatty acids such ascaprylic, capric, lauric, myristic, palmetic, stearic, oleic, linoleic,linolenic, abietic, hydroabietic, dehydroabietic, ricinoleic, and thelike; the naphthenic acids; the mixed fatty acids derived from vegetableoils such as coconut, palm, linseed, cottonseed, soya, tung, perilla,tall, corn, oiticica, and castor oils, the mixed fatty acids derivedfrom animal fats such as tallow fatty acids; the mixed fatty acidsderived from fish oils, such as herring, menhadden, salmon and sardineoils, and the like; the dimers, trimers, and tetramers of the foregoingunsaturated fatty acids such as the dimer acids from bodied soya beanoil, the trimer acids from bodied linseed oil, and the dimers, trimersand tetramers of fish oil fatty acids; and it being understood that toemploy unsaturated fatty acids set forth above to form soap usually suchacids must be at least partially and preferably totally hydrogenated.The designated salt of the carboxylic acids, having from 8 to 18 carbonatoms are preferred.

By the term synthetic detergents is meant herein the anionic and/ornon-ionic surface active agents or detergents. The anionic detergentsinclude alkyl (C -C aryl sulfonates, ethoxylated alkyl aryl sulfonates,alkyl (C -C sulfates including fatty acid alcohol sulfates, alkyl(,;C,,,) sulfonates, ethoxylated alcohol sulfates, alkyl and alkenylsulfonates including a-olefin sulfonates, the alkyl i.e. the monoordi-alkyl (Cg-C esters of sulphosuccinic acid. The compounds hereof areemployed in the form of alkaline salts, i.e., the sodium, potassium,ammonium or amine salts, of the corresponding free acids and include:sodium octyl sulphate, sodium monyl sulphate, sodium decyl sulphate,sodium undecyl sulphate, sodium dodecyl sulphate, sodium tridecylsulphate, sodium tetradecyl sulphate, sodium pentadecyl sulphate, sodiumhexadecyl sulphate, sodium heptadecyl sulphate, sodium octadecylsulphate,

sodium oleyl sulphate, sodium octyl sulphonate, so-

dium nonyl sulphonate, sodium decyl sulphonate, sodium undecylsulphonate, sodium dodecyl sulphonate, sodium tridecyl sulphonate,sodium tetradecyl sulphonate, sodium pentadecyl sulphonate, sodiumhexadecyl sulphonate, sodium -octadecyl sulphonate, sodium bleylsulphonate, sodium salt of di-octyl sulphosuccinate. sodium octylbenzene sulphonate, sodium nonyl benzene sulphonate. sodium decylbenzene sulphonate, sodium undecyl benzene sulphonate, sodium dodecylbenzene sulphonate, sodium tridecyl benzene sulphonate, sodiumtetradecyl benzene sulphonate, sodium pentadecyl benzene sulphonate,sodium hexadecyl benzene sulphonate, sodium heptadecyl benzene:sulphonate, sodium octadecyl benzene sulphonate, sodium tri (isopropyl)benzene sulphonate, sodium tri lisobutyl) benzene sulphonate, sodium tri(isopropyl) naphthalene sulphonate, sodium tri (isobutyl) naphthalenesulphonate, and combinations thereof, and the like.

The non-ionic detergents include alakanolamides, fatty amine oxides,ethylene oxide and propylene oxide condensates of long chain fattyalcohols, alkylphenols, fatty acids, mercaptans, amides, alkanolamides,amines, and more particularly the following represented by the formulaRS(C l-l O),.-H wherein R is a 8 to 12 carbon alkyl radical and n is aninteger from about 4 to 30.

It is most desirable that detergents be employed which arebiodegradable, that is have essentially straight chain alkyl groups.

Among the non-ionics are the Phuronic detergents of the general formulaPhenol ethylene oxide condensate (Type) (mols) Nonylphenol 9 Nonylphenoll2 Dinonylphenol 7 Dinonylphenol l5 Dodecylphenol 18 For furtherexamples of alkyl and alkaryl compounds which may be condensed withalkylene oxides such as ethylene oxide, propylene oxide and butyleneoxide, and for example of these alkyl oxide condensates phosphatedderivatives see for specific examples Papaloss U.S. Pat. No. 3,346,670the examples thereof being incorporated herein by reference.

Included herein are other ethylene oxide condensate products for exampledodecyl benzene sulfonamide condensed with 10 mols of ethylene oxide anddecyl sulfonamide with 6 mols of ethylene oxide and the like.

Included herein are the amine oxide detergents of the general formula RR R N-O in which R is a radical having 8 to 28 carbon atoms and to 2hydroxy groups and 0 to ether groups, R is a C to C alkyl radical and Ris selected from the alkyl radicals and the hydroxylkyl radicals having1 to 3 carbon atoms. For specific examples of the amine oxide detergentssee Deans 8 U.S. Pat. No. 3,523,088 the examples thereof beingincorporated herein by reference.

The anionic detergents include the phosphorous containing organicdetergent compounds such as the phosphate esters represented by thefollowing Alkyl-O P-(OMe) Aryl-O-P- (OMe) Q (Aryl-O-) -P-OMe Alkyl-O 9P-OMe Arylin which the alkyl has 8-27 carbon atoms and the aryl-0 is aphenoxy radical or a mono-, di-, or tri-alkylphenoxy radical in whichthe alkyl groups have 1 to 27 carbon atoms and Me is sodium, potassium,ammonium or substituted ammonium; the such detergents further includethe ethylene oxide and propylene oxide modifications of said organicphosphates as represented by the following formulae;

Alkyl-O- (C H O) in which the alkyl and aryl group limits are defined asfor the previous subclass of phosphoric acid esters, n and m areintegers from 1 to 40 and Me is sodium or potassium.

Included hereunder are other phosphorous containing detergents such asthe phosphonio carboxylates are described in U.S. Pat. No. 3,504,024which are hereby incorporated by reference.

Also the phosphine oxide detergents having the formula R R R PO in whichR is 10 to 28 carbon atoms radical with 0 to 2 hydroxyl groups and 0 to5 ether groups and R" is a C to C alkyl groups and R is an alkyl radicalor hydroxy alkyl radical with from I to 3 carbon atoms. For specificexamples of the phosphine oxide detergents see Dean's U.S. Pat. No.

3,523,088 the examples thereof being incorporated herein by reference.

By the term anionic polymeric dispersants or anionic polymericemulsifiers is meant polymers having organic acid groups as alkali metalsalts and as "such are water soluble or dispersable.

By the term non-ionic polymeric dispersants or nonionic polymericemulsifiers is'meant polymers which are watersoluble or dispersablewithout having organic acid and/or basic groups, the hydrophilic natureof these polymers being provided by the hydroxyl, or the like watersolublizing non-ionic groups.

The term polymeric dispersants or polymeric emulsifiers as employedherein is used in a limited sense and meant to include both anionicdispersants or emulsifiers and/or non-ionic dispersants or emulsifiers,however, such term excludes cationic dispersants or emulsifiers.

lncludedamong the polymeric dispersants or emulsifiers are thoseproduced by mass polymerization, or solution polymerization, suspensionpolymerization or, emulsion polymerization employing monomers yieldingpolymers that are water soluble or water dispersable or convertible tosuch form as with the aid of alkali. These polymers may be formed fromhydrophilic monomers, or from mixtures of hydrophilic monomers withhydrophobic monomers, provided the quantity of hydrophobic monomer isnot so high as to prevent the polymer from being, or being rendered,water soluble or dispersable. The hydrophilic monomers that may beemployed alone or with other monomers, in forming polymers that arewater solube of dispersable or convertible to such form may and includethe yellowing: (1) anionic hydrophilic monomers such as those containingcarboxylic, sulphonic acid or acid sulphate groups, or acid derivativesof phosphoric acid and (2) non-ionic hydrophilic monomers are thosecontaining e.g. hydroxyl, ether, hydroxy-ester, and/or amide groups.

The polymeric dispersants or emulsifiers employed in the presentinvention may be prepared from one or more of the hydrophilic monomers,even polymerizing monomers of the anionic and/or non-ionic, types in thesame hydrophilic polymer. Likewise the hydrophilic monomers may bepolymerized with hydrophobic monomers provided the amount of hydrophobicmonomer does not prevent the polymeric emulsifier from dissolving ordispersing in aqueous medium with or without the aid of a water solubebase, including, for example, the alkali-metal hydroxides, bicarbonatesand carbonates, and ammonia and its derivatives. The detergentcompositions hereof include the water soluble or dispersable polymers inthe presence of the alkaline silica and the electrolytes consisting ofalkali metal carbonates and/or bicarbonates.

A variety of hydrophilic polymer can be employed as polymericdispersants or emulsifiers especially watersoluble or water dispersiblepolyelectrolytes as for example those set forth'in Hendrick and MowryU.S. Pat. No. 2,625,529, and in which is described a number of materialswhich are synthetic watersoluble polyelectrolytes having a weightaverage molecular weight of at least 10,000 and having a structurederived by the polymerization of at least one monoolefinic compound,

found that lower molecular weights polyelectrolytes of at least 1,000 to2,000 and even as low as 700 can be employed as polymeric emulsifiers.The said Hendrick and Mowry patent is hereby incorporated by reference.Further, watersoluble anionic poiymeric dispersants which include saltsof polycarboxylic acid polymers and copolymers are referred to aspolyelectrolyte builder material consisting of water-soluble salts ofaliphatic polycarboxylic acid as in the patent to Diehl U.S. Pat. No.3,308,067 which is hereby incorporated by reference.

Useful in preparing the polymeric dispersants or emulsifiers hereof isvinylidene including vinyl monomer material of the following subclasses:

Monomers with carboxyl groups which includes monobasic organic acidssuch as acrylic, methacrylic cinnamic; propionic, crotonic and the likeacids; dibasic acids including catonic, mesaconic, citraconic, itaconic,aconitic, furmaric, maleic and the like acids, and the half esters ofthe dibasic acids esterified with ethylene glycol, propylene glycol andthe glycol ethers and the like;

Monomers with sulfonic groups which include styrene sulfonic acid(p-vinylbenzenesulfonic acid), toluene sulfonic acid and the like;

Monomers with hydroxyl and ester groups: the hydroxyalkal acrylates andmethacrylates which include hydroxyethyl acrylate and methacrylate,hydroxypropyl acrylate and methacrylate and the like;

Monomers with amide groups which include acylamide,N-isopropylmethacrylamide, N-methylacrylamide, N,N-diethylacrylamide,N-ethylacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide and acrylamide and thelike.

Polymers with hydrophylic groups:

the polyvinyl alcohols obtained by hydrolysis of polyvinyl acetate,polyvinyl alcohol copolymers, the N- alkyl-arylamide-vinyl alcoholcopolymers which can be prepared by the hydrolysis ofN-alkyl-acrylamide-vinyl acetate interpolymers (see U.S. Pat. No.2,798,047 which is incorporated herein by reference).

Vinylidene monomers with N-vinyl lactam groups such asl-vinyl-2-pyrrolidone, l-vinyl-5-methyl-2- pyrrolidone, l-vinyl-3-butylpyrrolidone, N-vinyl-S- methyl-S-ethyl pyrrolidone,N-vinyl-3,3,5-trimethyl pyrrolidone, N-vinyl-6butyl piperidone,1-vinyl-2- piperidone, N-vinyl-coprolactom, Nvinyl-7ethylcoprolactam,N-vinyl-3,5-dimethyl caprolactam,

N-vinyl-4-isopropyl caprolactam, and the like;

Vinylidene monomers with ether groups such as vinyl methyl ether, vinylbutyl ether, methyl isopropenyl ether, and the like;

Other polytectrolytes: copolymers of ethylene and maleic anhydride,copolymers, maleic anhydride and methyl vinyl ether, copolymers ofstyrene and maleic anhydride, hydrolized polyacrylonitrile, hydrolizedpolymethacrylontrile.

It is understood that the more hydrophobic vinylidene monomers set forthherein may have to be combined with more hydrophilic monomers of thoseset forth herein in order to provide interpolymers which are watersoluble or water dispersable.

Where the polymers including interpolymers are readily saponifiable asfor example may be the case with the ester polymers then the morealkaline combinations of alkaline silica and sodium carbonate are to beminimized and the alkaline silica-sodium bicarbonate combinations arepreferred.

When it is desirable to increase the hydrophobic nature of the polymersthen a hydrophobic vinylidene monomer may be selected from the knownvinylidene monomers and the term vinylidene monomer as used herein ismeant to include vinyl monomer.

The polymerization technics for the monomers selected herein arewell-known to the art as are likewise the polymerization catalysts suchas, for example, the organic peroxides, e.g. benzoyl peroxide, theorganic hydroperoxides, e.g. cumene hydroperoxide, the azocatalysts e.g.azo-bis-isobutyronitrile, the inorganic peroxygen compounds, e.g.potassium persulfate or the hydrogen peroxide and the like.

Anionic and/or non-ionic emulsifiers may be used to prepare thepolymeric detergents hereof.

The terms dried and drying herein are employed in the sense in whichthey are employed in the drying of soap and detergent products, i.e. thesense of removing excess water as by evaporation, spray drying, reverseosmosis or other membrane methods, or other applicable procedures, thedrying being effected sufficiently to produce a commercially usefulproduct.

The following examples of specific embodiments of the invention are setforth to facilitate practice of the same, and are to be regarded asillustrative and not restrictive of the invention, the scope of which ismore particularly pointed out and distinctly claimed hereinafter.

EXAMPLES EXAMPLE 1 This example was carried out in the following manner:to 2000 ml. of a 41 Be aqueous solution containing 4 mols sodiumsilicate of the composition represented by Na O(SiO was added 14 litersof water and placed in a precipitator vessel equipped with an agitatorand the temperature thereof raised to 79 C. To this hot aqueous sodiumsilicate solution was gradually added 4 liters of an aqueous solutioncontaining 4 mols of sodium carbonate and concurrently therewith butover a more extended period was added 4 mols of carbon dioxide. The timeschedule of these additions is shown in Table 1.

12 On spray drying of the resulting slurry of wet precipitated alkalinesilica pigment having bound alkali and free alkali therein, a detergentadjuvant having the fol lowing composition is obtained:

Detergent Adjuvant Composition Silica pigment (with 2% bound alkali)Sodium carbonate "Cale. anhydrous basis.

EXAMPLE 2 2(a). Example 1 is repeated in pound mols and prior to drying875 lbs. of the sodium salt of dodecyl benzene sulphonate (DDBS) isadded as an aqueous solution and after thorough mixing the composition,on spray drying, yields the following product:

Detergent Composition Wt., lbs.* Wt.,

Sodium salt DDBS 875 35.0 Silica Pigment (with 2% bound alkali as Na O)787 31.6 Sodium carbonate 832 33.4

Calc. anhydrous basis.

2(b). Example 1 is repeated in pound mols with the CO addition,continued until the acidulation reaches 150% and 875 lbs. of the sodiumsalt of dodecyl benzene (DDBS) is then added as aqueous solution,together with 62 lbs. of carboxy methyl cellulose (CMC) and an opticalbrightening agent, 5 lbs., and the combination is spray dried yieldingthe following product:

To a stainless steel reactor with agitator is added 1400 lbs. of water,32.7 lbs. of dodecyl benzene sulfonate, and 4 lbs. sodium hydroxide andthe mixture raised to C. There is then added 310 lbs. equivalent to 200mols Na O(SiO of 41 Be commerical sodium silicate solution. Afterthorough mixing carbon dioxide is introduced through a lead tube to thebottom of the reactor and over a period of 600 minutes 200 mols ofcarbon dioxide is introduced at a constant rate. On completion of theacidification with carbon dioxide the product is spray dried and has thefollowing composition'.

Thecornbind oifo .he 'w t silica slurry and the de tergent pasteonspraydr'ylng yields a product of the following composition zDetergeniComposition Wt, 1b.* Wt, /r* Detergent Composition Wt. grams*Wt. 7r*

Sodium salt Of DDBS 34.9 20.9 Silica Pigment (with 2% bound 'P smei t(with 2% 5 alkali) 1,182 37.5 boimd alkal as N320 Sodium Carbonate 1.21438.5 Sodlum Carbonate Sodium salt dodecylbenzene 167.0 100.0 sulphonate640 20.2 V Oleic acid diethanolamidc 45 1.4 *Calc; anhydrous basisCarboxy methyl cellulose 75 2,4 3,156 100.0

4 *Calc. anhydrous basis In this example 3000 ml. of type N sodiumsilicate (Na O(SiO containing 6 mols of Na O is diluted EXAMPLE 6 with 6liters of water to which is added 636 g. (6 mols) ,of sodium carbonatedissolved in 8 liters of water at 60 A 270 gallon i f equ 1pped wlthdnveri 50 and the combination is placed in a ceramic vessel r.p.m. lowshear stirring arm 18 charged with 780 liters and agitated by a 3 bladed3" propeller driven 600 of 80 C. water, and 65 kllosof sodium soap oftallow The acidulating agent consists of fatty acids is added andpermitted to dissolve, followed mols) of sodium bicarbonate dissolved in15 liters of 20 y 144 kilos of Commercial Be Sodium Silicate waterat 0C, The id i i agent i dd d to th taining 200 mols of the compositionexpressed by the dilute sodium silicate in a controlled manner accordingformula Na O/(SiO The mixture is thoroughly to Table 11 herein. blendedwith the aid of the agitator. While the solution TABLE II is held at 80i 10 C. a submerged combustion burner supplied with propane and air isignited and submerged Time (minutes Acidulation (mols NaHCOa below thesurface of the solutlon. The submerged comu u l cumulative) bustionburner is operated at a relat1vely constant rate 0 so that after 150minutes the acidulation had prog- 62 1.1 ressed to 34%, i.e. 68 mols ofcarbon dioxide had been absorbed by the sodium silicate solution. 1293.9 165 6 0 1n the examples hereof heat can be supplied by vesselheating acket 180 or heating coils and any source of carbon dioxide maybe used. 9 I The acidulation at 80 C. is continued for 510 min- 219 uteswith the aid of the submerged combustion burner Initial precipitation ofsilica. until after a total of 660 minutes the acidulation has 1 reached100%, i.e. 200 mols of carbon dioxide has The slurry of precipitatedsilica having bound alkali been absorbed by the silica slurry.Throughout the forand free alkali, 0n y g yields a Product Of thefOllOW- mation of the silica slurry the slow speed, low shear stirgJCOmYPOSItIOHI 40 rer is used, and from time to time water is added tocompensate for the loss thereof due to operation of the V burner. SilicaCom osltion Wt. rams* WL. 72* I i i V g The resulting product, whendried, has the followlng Silica Pigmenttwith 2% bound o iti alkali)1.182 48.5 v

Sodiurit Carbonate 1,236 51,5

2,418 100.0 v7 Detergent Composition Wt. Ki1os* WI. 7c* Cale. anhydrousbasis Silica pigment (with 2% bound alkali) 39.4 31.4 Sodium carbonate21.1 16.8 EXAMPLE 5 Sodium tallow fatty acid soap 65.0 51,8 Example 4 isrepeated, however prior to drying, the 125.5 100.0 silica slurrycontaining bound alkali and free alkali C I h d b there is addeddetergent paste formulated as follows: mus

EXAMPLE 7 DETERGENT PASTE FORMULATION I d w To a 270 gallon reactor withstirrer is charged 680 grams liters of 80 C. water and 144 kilos ofcommercial 41 Linear dodecylbenzene sulpho'nate 600 Be sodium silicatecontaining 200 mols of sodium sili- Caustic Soda 75 ,Sodium hypochloritea Cate of formula 2 )a.az n he mixture is Oleic acid diethanolamide- 45thoroughly blended. With the aid of a submerged comgfgzg mcthyl cellulme2 3 bustion burner carbon dioxide is supplied to the reactor 1 at aconstant rate at a temperature of 80 C. and after 660 minutes 200 molsof carbon dioxide has been reacted with the sodium silicate solution toyield alkaline silica and sodium-carbonate in the following proportions:

Detergent Adjuvant Composition Wt., Kilos* Wt. 7r" Detergent Compositione Sodium salt vinyl methyl iil za l ih (wuh 2% bound 3 4 65 5 Othermaleic anhydride 30 18 5 copolymer bodium carbonate Zl 35 sodium salt ofDDBS 5 11 60.5 100.0 Silica pigment (2% bound alkali) 85 52.4 Talcanhydrous ham Sodium carbonate 42 26.0 162 100.0

8 Cale. anhydrous basis.

iExam 1e 7 was re eated exce t that the 20 kilos of p p p EXAMPLE lldodecylbenzene sulfonic acid was replaced with 20 kilos (l00% activebasis) of nonyl phenol condensed In an agitated vessel is added 1400lbs. of water, 310 i h 9 10 l h l id d h ble d th lbs. of aqueous sodiumsilicate containing 200 mols of oughly mixed and spray dried and has thefollowing z z)a.2zr f P P *r?Q Composition; sodium salt of polyacrylicacid and after mixing the temperature is raised to 60 C. and 300 mols ofcarbon dioxide absorbed over a period of 900 minutes, then is DetergentComposition Wt. Kilos* Wt. added 17.9 lbs. of alipal 233** containing28% of the 27 b d [k l. 39 4 48 8 sodium salt of ethoxylated nonylphenol sulfonate and 355,1; g g g 2612 the combination blended anddried. The product had Nonyl phenol with 9-10 the following composition:

molecules of ethylene 25 oxide 20.0 25

loo-0 Detergent Composition WL, lbs.* Wt.,%*

"(Talc anhydrous basis Sodium polyacrylic acid salt 2O 12 30 Sodiumalkyl phenol ethoxylate sulfonate 5 3 EXAMPLE 9 Silica pigment (1% boundalkali) 86 51 in an agitated vessel is added 1400 lbs. of water, 310 sdiu carbonate i2 3 Sodium bicarbonate 33 20 lbs. of aqueous sodiumsilicate contain ng 200 mols of Trisodium phosphate 10 6 N8 O(SlO and 50lbs. of poly(sodium styrene sul- 166 100 fonate) and after adequatemixing the solution temper- 35 r o 'Thtd h ht b ld'th d t'lh ht,tt mmwas ralsed 75 C Acldulatlon Carbon anr3in";ri'ief fi .iZr.2"3ooi$32.2;...3055833510325;rii riei nirff xide was carried out at a relativeconstant rate so that ?odium triplt osphaie and the like. The saidphosphate salts may be added after ormat'on o the si ica. after 800minutes 300 mols of carbon dioxide had been "1mm, product of GeneralAniline corp, absorbed. Then was added 10 lbs. of nonyl phenol con- 40tiensed with 9.5 mols ethylene oxide and after uniform All aboveexamples of detergent compositions may mixing the blend was spray dried.The product had th also be practiced with addition of conventional soapfollowing composition: and/or detergent additives, usually in minorproportions, such as perfumes, disinfectants, bleaches, brighteners,abrasives, enzymes, solvents and oils, rnedicating Delergem Compositionlbs? ingredients, and the like, without departing from the 5 It 1 Sinvention.

urn S O renc o f g y y 25 While there have been described herein whatare at Alkyl phenol ethoxylate 1O 5 present considered preferredembodiments of the in- 5ilicallpiglri;ent 1% bound 86 43 5O vention, itwill be obvious to those skilled in the art that i' 2] l SodiumCarbonate 21 I05 modifications and changes may be made therein with-Sodium bicarbonate 33 16.5 out departing from the essence of theinvention. It is 200 100.0 therefore understood that the exemplaryembodiments are illustrative and not restrictive of the invention, the

Talc scope of which is defined in the appended claims, and

that all modifications that come within the meaning EXAMPLE 10 and rangeof equivalents of the claims are intended to D I be included therein. inan agitated vessel is added 1400 lbs. of water, 3 l0 1 claim. lbs. ofaqueous sodium silicate containing 200 mols of A process for preparing adetergent adjuvam Na O(SiO and 30 lbs. of the sodium salt of thecobination which comprises; P y of W methyl ether and malelc anhydfldera. forming an aqueous solution of water soluble alkali and afterblending and the temperature raised to 80 metal ili CH 200 mols ofcarbon dioxide was reacted over a peb. adding to said solutionsufficient reactant selected :riod of 500 minutes. Then 5 lbs. ofdodecylbenzene sulfrom the class consisting of carbon dioxide andalphonic acid sodium salt was added and the blend spray dried and theproduct had the following composition:

kali metal bicarbonate to form therewith a solution of electrolyteselected from the alkali metal carbonates and bicarbonates and aprecipitate of alkaline silica pigment therein containing from 0.2 to40% bound alkali by weight based on the silica of I the pigment, and

' c. recovering and essentially drying together the combination of saidalkaline silica pigment and at least 25% drybasis, by weight, of theelectrolyte resulting from step'('b).

2. A process as claimed in claim 1, in which step (b) is conducted toprovide said solution with electrolyte consisting at least 2 mol percentof alkali metal bicarbonate.

3. A process as claimed in claim 1, in which step (b) is conducted toprovide said solution with electrolyte consisting at least mol percentof alkali metal bicarbonate.

4. A process as claimed in claim 1, in which step (b) is conducted toprovide said solution with electrolyte consisting at least 30 molpercent of alkali metal bicarbonate.

5. A process as claimed in claim 1, in which step (b) is conducted toprovide said solution with electrolyte consisting at least 50 molpercent of alkali metal bicarbonate.

6. A process as claimed in claim 1, in which step (b) is conducted toprovide said solution with electrolyte consisting at least 90 molpercent of alkali metal bicarbonate.

7. A process for preparing a detergent composition which comprises:

a. forming an aqueous solution of water soluble alkali metal silicatecontaining water soluble material selected from the class consistingessentially of the members of the following groups: Group (I) soaps;Group (II) synthetic anionic detergents; Group (Ill) nonionicdetergents; and combinations of two or more of said members; in a ratioin the range of 5:95 to 95:5 parts dry basis, by weight, based on thesilica content as SiO b. adding to said solution sufficient reactantselected from the class consisting of carbon dioxide and alkali metalbicarbonate to form therewith a solution of said water soluble materialand electrolyte selected from the alkali metal carbonates andbicarbonates with a precipitate of alkaline silica pigment thereincontaining from 0.2 to 40% bound alkali by weight based on the silica ofthe pigment, and

c. recovering the products of reaction (b) as a detergent compositionincorporating said electrolyte and said alkaline silica pigmentprecipitate 8. A process as claimed in claim 7, in which in step (a)less than the maximum ratio of said water soluble material to silica isemployed, and in step (c) the detergent adjuvant combination is mixedwith further material selected from the members of said class andcombinations thereof, in an amount which combined with that included instep (a) lies in the aforesaid ratio range.

9. A process as claimed in claim 7, in which, in step (c) the furthermaterial comprises material selected from the sub-class consisting ofthe members of Groups (I), and (II) which is formed in the presence ofthe silica pigment by reaction of the corresponding free acid withalkalinity of the combination resulting from step (b).

10. A composition consisting essentially of a mixture of the followingcomponents (I) and (II):

I. A detergent adjuvant combination consisting essentially of:

a. an alkaline hydrated silica pigment combined with b. an electrolyte,

c. said alkaline silica pigment having a surface area in the range of 25to about 500 meters per gram and having been prepared in aqueous mediumby the acidulation of an aqueous solution of alkali metal silicate, andhaving, prior to drying thereof, been combined with said electrolyte,

d. said electrolyte having been selected from the class consisting ofthe alkali metal carbonates and bicarbonates, and being present in anamount in the range of 0.1 to 20 parts of electrolyte per part of silicapigment, as SiO by weight and e. said combination of said electrolyteand pigment in aqueous medium having been dried, and

II. water soluble material selected from the class consistingessentially of the'members of the following groups: Group (I) soaps;Group (II) synthetic anionic detergents; Group (III) non-ionicdetergents; and combinations of two or more of said members; in a ratioin the range of 5:95 to :5 parts dry basis, by weight, based on thesilica content of the adjuvant combination as SiO 11. A composition asclaimed in claim 10, said hydrated silica pigment and at least a part ofsaid electrolyte having been prepared in the presence of the said watersoluble material.

12. A composition as claimed in claim 10, in which the water solublematerial comprises at least 5 parts per 100, dry basis by weight, ofnon-ionic detergent from Group (III).

13. A composition as claimed in claim 10, in which the compositionfurther comprises at least 5 parts per 100, dry basis by weight, ofnon-ionic polymeric emulsifier material.

14. A process for preparing a detergent adjuvant combination whichcomprises:

a. forming an aqueous solution of water soluble alkali metal silicate,

b. adding to said solution sufficient reactant selected from the classconsisting of carbon dioxide and alkali metal bicarbonate to formtherewith a solution of electrolyte selected from the alkali metalcarbonates and bicarbonates and a precipitate of alkaline silica pigmenttherein containing from 0.2 to 40% bound alkali by weight based on thesilica of the pigment, and

c. recovering and essentially drying together the combination of saidalkaline silica pigment and at least 25% dry basis, by weight, of theelectrolyte resulting from step (b), said recovery including spraydrying.

15. A process for preparing a detergent adjuvant combination whichcomprises:

a. forming an aqueous solution of water soluble alkali metal silicate,

b. adding to said solution sufficient reactant selected from the classconsisting of carbon dioxide and alkali metal bicarbonate to formtherewith a solution of electrolyte selected from the alkali metalcarbonates and bicarbonates and a precipitate of alkaline silica pigmenttherein containing from 0.2 to

40% bound alkali by weight based on the silica of the pigment, and

c. recovering and essentially drying together in combination saidpigment and substantially all of the electrolyte resulting from step(b), as the detergent adjuvant combination.

16. A process for preparing a detergent adjuvant combination whichcomprises:

a. forming an aqueous solution of water soluble alkali metal silicate,

b, adding to said solution sufficient reactant selected from the classconsisting of carbon dioxide and alkali metal bicarbonate to formtherewith a solution of electrolyte selected from the alkali metalcarbonates and bicarbonates with a precipitate of alkaline silicapigment therein containing from 0.2 to 40% bound alkali by weight basedon the silica of the pigment, and recovering together said alkalinesilica pigment and at least 25% dry basis, by weight, of the electrolyteresulting from step (b), in combination, as .a detergent adjuvantcombination, said recovery including incorporating said adjuvantcombination with detergent material selected from the class consistingessentially of the members of the following groups: Group (I) soaps;Group (II) synthetic anionic detergents; Group (III) non-ionicdetergents; and combinations of two or more of said members; in a ratioin the range of 5:95 to 95:5 parts dry basis, by weight, based on thesilica content as SiO thereby forming a detergent compositionincorporating said detergent adjuvant combinationv 17. A process asclaimed in claim 16, in which the detergent adjuvant combination, instep without having been dried following step (b), is mixed with anaqueous dispersion of said detergent material.

18. A process as claimed in claim 17, in which the recovery of theproduct is effected by spray-drying of the mixed adjuvant combinationand aqueous dispersion.

19. A process as claimed in claim 16, in which there is alsoincorporated in the detergent and adjuvant combination material selectedfrom the class consisting of the anionic polymeric emulsifiers and thenon-ionic polymeric emulsifiers.

20. A process for preparing a detergent adjuvant combination whichcomprises:

a. forming an aqueous solution of water soluble alkali metal silicate.

b. adding to said solution sufficient reactant selected from the classconsisting of carbon dioxide and alkali metal bicarbonate to formtherewith a solution of electrolyte selected from the alkali metalcarbonates and bicarbonates with a precipitate of alkaline silicapigment therein containing from 0.2 to 40% bound alkali by weight basedon the silica of the pigment, and c. recovering and essentially dryingtogether the combination of said alkaline silica pigment and at least25% dry basis, by weight, of the electrolyte resulting from step (b), incombination, as a detergent adjuvant combination, said recoveryincluding incorporating said adjuvant combination with detergentmaterial selected from the class consisting essentially of the membersof the following groups: Group (I) soaps; Group (II) synthetic anionicdetergents; Group (Ill) non-ionic detergents; and combinations of two ormore of said members; in a ratio in the range of 5:95 to 95:5 parts drybasis, by weight, based on the silica content as SiO thereby forming adetergent composition incorporating said detergent adjuvant combination,and

d. in which the detergent material comprises material selected from thesub-class consisting of the members of Groups (I) and (II) which isformed in the presence of the silica pigment by reaction of thecorresponding free acid with alkalinity of the combination resultingfrom step (b).

21. A process for preparing a detergent adjuvant combination whichcomprises:

a. forming an aqueous solution of water soluble alkali metal silicate,

b. adding to said solution sufficient reactant selected from the classconsisting of carbon dioxide and alkali metal bicarbonate to formtherewith a solution of electrolyte selected from the alkali metalcarbonates and bicarbonates with a precipitate of alkaline silicapigment therein containing from 0.2 to 40% bound alkali by weight basedon the silica of the pigment, and

c. recovering and essentially drying together the combination of saidalkaline silica pigment and at least 25% dry basis, by weight, of theelectrolyte resulting from step (b), in combination, as a detergentadjuvant combination, said recovery including incorporating saidadjuvant combination with detergent material selected from the classconsisting essentially of the members of the following groups: Group (I)soaps; Group (II) synthetic anionic detergents; Group (III) non-ionicdetergents; and combinations of two or more of said members; in a ratioin the range of 5:95 to 95:5 parts dry basis, by weight, based on thesilica content as SiO thereby forming a detergent compositionincorporating said detergent adjuvant combination, and

d. in which the detergent material comprises a soap formed in thepresence of the silica pigment by saponification of fatty acid glyceridewith the aid of alkalinity of the combination resulting from step

1. A PROCESS FOR PREPARING A DETERGENT ADJUVANT COMBINATION WHICHCOMPRISES: A. FORMING AN AQUEOUS SOLUTION OF WATER SOLUBLE ALKALI METALSILICATE, B. ADDING TO SAID SOLUTION SUFFICIENT REACTANT SELELCTED FROMTHE CLASS CONSISTING OF CARBON DIOXIDE AND ALKALI METAL BICARBONATE TOFORM THEREWITH A SOLUTION OF ELECTROLYTE SELECTED FROM THE ALKALI METALCARBONATES AND BICARBONATES AND A PRECIPITATE OF ALKALINE SILICA PIGMENTTHEREIN CONTAINING FROM 0.2 TO 40% BOUND ALKALI BY WEIGHT BASED ON THESILICA OF THE PIGMENT, AND C. RECOVERING AND ESSENTIALLY DRYING TOGETHERTHE COMBINATION OF SAID ALKALINE SILICA PIGMENT AND AT LEAST 25% DRYBASIS, BY WEIGHT, OF THE ELECTROLYTE RESULTING FROM STEP B).
 2. Aprocess as claimed in claim 1, in which step (b) is conducted to providesaid solution with electrolyte consisting at least 2 mol percent ofalkali metal bicaRbonate.
 3. A process as claimed in claim 1, in whichstep (b) is conducted to provide said solution with electrolyteconsisting at least 10 mol percent of alkali metal bicarbonate.
 4. Aprocess as claimed in claim 1, in which step (b) is conducted to providesaid solution with electrolyte consisting at least 30 mol percent ofalkali metal bicarbonate.
 5. A process as claimed in claim 1, in whichstep (b) is conducted to provide said solution with electrolyteconsisting at least 50 mol percent of alkali metal bicarbonate.
 6. Aprocess as claimed in claim 1, in which step (b) is conducted to providesaid solution with electrolyte consisting at least 90 mol percent ofalkali metal bicarbonate.
 7. A process for preparing a detergentcomposition which comprises: a. forming an aqueous solution of watersoluble alkali metal silicate containing water soluble material selectedfrom the class consisting essentially of the members of the followinggroups: Group (I) soaps; Group (II) synthetic anionic detergents; Group(III) nonionic detergents; and combinations of two or more of saidmembers; in a ratio in the range of 5:95 to 95:5 parts dry basis, byweight, based on the silica content as SiO2, b. adding to said solutionsufficient reactant selected from the class consisting of carbon dioxideand alkali metal bicarbonate to form therewith a solution of said watersoluble material and electrolyte selected from the alkali metalcarbonates and bicarbonates with a precipitate of alkaline silicapigment therein containing from 0.2 to 40% bound alkali by weight basedon the silica of the pigment, and c. recovering the products of reaction(b) as a detergent composition incorporating said electrolyte and saidalkaline silica pigment precipitate.
 8. A process as claimed in claim 7,in which in step (a) less than the maximum ratio of said water solublematerial to silica is employed, and in step (c) the detergent adjuvantcombination is mixed with further material selected from the members ofsaid class and combinations thereof, in an amount which combined withthat included in step (a) lies in the aforesaid ratio range.
 9. Aprocess as claimed in claim 7, in which, in step (c) the furthermaterial comprises material selected from the sub-class consisting ofthe members of Groups (I), and (II) which is formed in the presence ofthe silica pigment by reaction of the corresponding free acid withalkalinity of the combination resulting from step (b).
 10. A compositionconsisting essentially of a mixture of the following components (I) and(II): I. A detergent adjuvant combination consisting essentially of: a.an alkaline hydrated silica pigment combined with b. an electrolyte, c.said alkaline silica pigment having a surface area in the range of 25 toabout 500 meters per gram and having been prepared in aqueous medium bythe acidulation of an aqueous solution of alkali metal silicate, andhaving, prior to drying thereof, been combined with said electrolyte, d.said electrolyte having been selected from the class consisting of thealkali metal carbonates and bicarbonates, and being present in an amountin the range of 0.1 to 20 parts of electrolyte per part of silicapigment, as SiO2, by weight and e. said combination of said electrolyteand pigment in aqueous medium having been dried, and II. water solublematerial selected from the class consisting essentially of the membersof the following groups: Group (I) soaps; Group (II) synthetic anionicdetergents; Group (III) non-ionic detergents; and combinations of two ormore of said members; in a ratio in the range of 5:95 to 95:5 parts drybasis, by weight, based on the silica content of the adjuvantcombination as SiO2.
 11. A composition as claimed in claiM 10, saidhydrated silica pigment and at least a part of said electrolyte havingbeen prepared in the presence of the said water soluble material.
 12. Acomposition as claimed in claim 10, in which the water soluble materialcomprises at least 5 parts per 100, dry basis by weight, of non-ionicdetergent from Group (III).
 13. A composition as claimed in claim 10, inwhich the composition further comprises at least 5 parts per 100, drybasis by weight, of non-ionic polymeric emulsifier material.
 14. Aprocess for preparing a detergent adjuvant combination which comprises:a. forming an aqueous solution of water soluble alkali metal silicate,b. adding to said solution sufficient reactant selected from the classconsisting of carbon dioxide and alkali metal bicarbonate to formtherewith a solution of electrolyte selected from the alkali metalcarbonates and bicarbonates and a precipitate of alkaline silica pigmenttherein containing from 0.2 to 40% bound alkali by weight based on thesilica of the pigment, and c. recovering and essentially drying togetherthe combination of said alkaline silica pigment and at least 25% drybasis, by weight, of the electrolyte resulting from step (b), saidrecovery including spray drying.
 15. A process for preparing a detergentadjuvant combination which comprises: a. forming an aqueous solution ofwater soluble alkali metal silicate, b. adding to said solutionsufficient reactant selected from the class consisting of carbon dioxideand alkali metal bicarbonate to form therewith a solution of electrolyteselected from the alkali metal carbonates and bicarbonates and aprecipitate of alkaline silica pigment therein containing from 0.2 to40% bound alkali by weight based on the silica of the pigment, and c.recovering and essentially drying together in combination said pigmentand substantially all of the electrolyte resulting from step (b), as thedetergent adjuvant combination.
 16. A process for preparing a detergentadjuvant combination which comprises: a. forming an aqueous solution ofwater soluble alkali metal silicate, b. adding to said solutionsufficient reactant selected from the class consisting of carbon dioxideand alkali metal bicarbonate to form therewith a solution of electrolyteselected from the alkali metal carbonates and bicarbonates with aprecipitate of alkaline silica pigment therein containing from 0.2 to40% bound alkali by weight based on the silica of the pigment, and c.recovering together said alkaline silica pigment and at least 25% drybasis, by weight, of the electrolyte resulting from step (b), incombination, as a detergent adjuvant combination, said recoveryincluding incorporating said adjuvant combination with detergentmaterial selected from the class consisting essentially of the membersof the following groups: Group (I) soaps; Group (II) synthetic anionicdetergents; Group (III) non-ionic detergents; and combinations of two ormore of said members; in a ratio in the range of 5:95 to 95:5 parts drybasis, by weight, based on the silica content as SiO2, thereby forming adetergent composition incorporating said detergent adjuvant combination.17. A process as claimed in claim 16, in which the detergent adjuvantcombination, in step (c), without having been dried following step (b),is mixed with an aqueous dispersion of said detergent material.
 18. Aprocess as claimed in claim 17, in which the recovery of the product iseffected by spray-drying of the mixed adjuvant combination and aqueousdispersion.
 19. A process as claimed in claim 16, in which there is alsoincorporated in the detergent and adjuvant combination material selectedfrom the class consisting of the anionic polymeric emulsifiers and thenon-ionic polymeric emulsifiers.
 20. A PROCESS FOR PREPARING A DETERGENTADJUVANT COMBINATION WHICH COMPRISES: A. FORMING AN AQUEOUS SOLUTION OFWATER SOLUBLE ALKALI METAL SILICATE, B. ADDING TO SAID SOLUTION OF WATERSOLUBLE ALKALI METAL THE CLASS CONSISTING OF CARBON DIOXIDE AND ALKALIMETAL BICARBONATE TO FORM THEREWITH A SOLUTION OF ELECTROLYTE SELECTEDFROM THE ALKALI METAL CARBONATES AND BICARBONATES WITH A PRECIPITATE OFALKALINE SILICA PIGMENT THEREIN CONTAINING FROM 0.2 TO 40% BOUND ALKALIBY WEIGHT BASED ON THE SILICA OF THE PIGMENT, AND C. RECOVERING ANDESSENTIALLY DRYING TOGETHER THE COMBINATION OF SAID ALKALINE SILICAPIGMENT AND AT LEAST 25% DRY BASIS, BY WEIGHT, OF THE ELECTROLYTERESULTING FROM STEP (B), IN COMBINATION, AS A DETERGENT ADJUVANTCOMBINATION, SAID RECOVERY INCLUDING INCORPORATING SAID ADJUVANTCOMBINATION WITH DETERGENT MATERIAL SELECTED FROM THE CLASS CONSISTINGESSENTIALLY OF THE MEMBERS OF THE FOLLOWING GROUPS: GROUP (I) SOAPS;GROUP (II) SYNTHETIC ANIONIC DETERGENTS; TWO OR MORE OF SAID MEMBERS; INA RATIO IN THE RANGE OF 5:95 TO 95:5 PARTS DRY BASISM BY WEIGHT, BASEDON THE SILICA CONTENT AS SIO2, THEREBY FORMING A DETERGENT COMPOSITIONINCORPORATING SAID DETERGENT ADJUVANT COMBINATION, AND D. IN WHICH THEDETERGENT MATERIAL COMPRISES MATERIAL SELECTED FROM THE SUB-CLASSCONSISTING OF THE MEMBERS OF GROUPS (I) AND (II) WHICH IS FORMED IN THEPRESENCE OF THE SILICA PIGMENT BY REACTION OF THE CORRESPONDING FREEACID WITH ALKALINITY OF THE COMBINATION RESULTING FROM STEP (B).
 21. Aprocess for preparing a detergent adjuvant combination which comprises:a. forming an aqueous solution of water soluble alkali metal silicate,b. adding to said solution sufficient reactant selected from the classconsisting of carbon dioxide and alkali metal bicarbonate to formtherewith a solution of electrolyte selected from the alkali metalcarbonates and bicarbonates with a precipitate of alkaline silicapigment therein containing from 0.2 to 40% bound alkali by weight basedon the silica of the pigment, and c. recovering and essentially dryingtogether the combination of said alkaline silica pigment and at least25% dry basis, by weight, of the electrolyte resulting from step (b), incombination, as a detergent adjuvant combination, said recoveryincluding incorporating said adjuvant combination with detergentmaterial selected from the class consisting essentially of the membersof the following groups: Group (I) soaps; Group (II) synthetic anionicdetergents; Group (III) non-ionic detergents; and combinations of two ormore of said members; in a ratio in the range of 5:95 to 95:5 parts drybasis, by weight, based on the silica content as SiO2, thereby forming adetergent composition incorporating said detergent adjuvant combination,and d. in which the detergent material comprises a soap formed in thepresence of the silica pigment by saponification of fatty acid glyceridewith the aid of alkalinity of the combination resulting from step (b).